Hard Soft Acid Base Theory

H Acids: small, highly (+) ions

low polarizability, fewer e
e.g. Fe3+ Co3+ Cr3+

H Bases: small, high donor atoms

low polarizability
e.g. F, N- and O-donors

S Acids: large, less (+) ions

S Bases: large, lower donor atoms
high polarizability, more e
high polarizability
e.g. Pt2+ Ag+ Au+
e.g. I, C- P- and S- donors
Metal ions: softness as Mrow and Mcolumn, softness as n+
Ligands: hardness as Lrow and column
Hard Acids
H+ Gr1 M+ Gr 2 M2+ Gr 13 M3+ Ti4+
V5+ VO2+ Cr3+ Cr2+
Mn2+ Fe3+ Co3+
Hard Bases
F Cl HO RO RCO2 CO3 NO3
SO42 ox2 H2O ROH NH3 RNH2
Intermediate Acids
Fe2+ Co2+ Ni2+ Cu2+ Zn2+
Ru3+ Ir3+ Rh3+
Intermediate Bases
py N3 NO2 SO32 Br NCS
Soft Acids
Pd2+ Pt2+ Cu+ Ag+ Au+
Cd2+ Hg+ Hg2+ Tl+ Pb2+
Soft Bases
I H R CN CNR CO
SCN RS RSH R2S R3P alkene arene

harder

A qualitative observation:
Hard likes hard, soft likes soft
e.g. AHBS + ASBH AHBH + ASBS will have K > 1
e.g. ML bond strengths: F > Cl > Br > I for Zn2+ F < Cl < Br < I for Hg2+

softer

ionic radii, Oh M2+

100
95

rion (pm)

90
85

HS

80
75
70

LS

65
60

M2+ Ca Sc Ti V Cr
dn 0 1 2 3 4
CFSE HS (Dq) 0 4 8 12 6
CFSE LS (Dq)
16

Mn
5
0
20

Fe
6
4
24

Co Ni Cu Zn
7 8 9 10
8 12 6 0
18

Hydration Enthalpies, M2+

Irving Williams Series

[M(H2O)6]2+ + L [M(L)(H2O)n]2+ + n H2O

M2+(g) + 6 H2O [M(H2O)6]2+(aq)

3000

20.0
18.0

2950

Hhydr (kJ/mol)

16.0

log K1

14.0
12.0

[EDTA]4
en
NH3

10.0
8.0
6.0
4.0

2900
2850
2800
2750

2.0
2700

0.0
Mn

Fe

Co

M2+
dn
CFSE (Dq)
rion
stability

Ni

Cu

Mn
5
0

Mn

Zn

Fe
6
4
>
<

Co
7
8
>
<

Ni
8
12
>
<

<

Fe

Co

Cu
9
6

Zn
10
0
<
>

Ni

Cu

Zn